Solid-State Synthesis and Optical Studies of Water-Stable Pb2+-Doped Mn2+ Complexes.

The limited Mn2+ doping that occurs in lead halide perovskites has been widely described, while the Pb2+ doping that occurs in Mn2+ halide perovskites has not been studied well. Generally, a large amount of doping of Mn2+ in lead halide perovskite degrades the perovskite structure; eventually, high orange luminescence of Mn2+ dopant has not been achieved. In our present study, we followed a reverse strategy, i.e., Pb2+ doping in Mn2+ halide perovskites, to increase the amount of Mn2+ in halide perovskites through the high-energy ball milling method. This strategy yields bright-fluorescence orange light-emitting Mn2+-doped perovskite with a Mn/Pb ratio of 95%, which is the highest among Mn2+-doped perovskites. Zero-dimensional (0D) Mn2+ perovskites and two-dimensional (2D) Pb2+-doped Mn2+-based perovskites were successfully synthesized and characterized. During the mechanochemical engineering, Pb2+ ions partially occupy the site of Mn2+ ions and act as a luminescence activator. Mn2+-based 2D perovskites with the proper amounts of Pb2+ ions as dopant ions and phenylethylammonium (PEA+) as dielectric organic cations show enhanced stability in water. The dual-emissive properties of these 2D-Pb2+-doped Mn2+-based perovskites were also investigated by using single-particle imaging fluorescence. We believe that these findings will pave the way for designing eco-friendly dimension and bandgap tunable layered perovskites.

Remarkably Enhanced Lattice Oxygen Participation in Perovskites to Boost Oxygen Evolution Reaction.

Enhancing the participation of the lattice oxygen mechanism (LOM) in several perovskites to significantly boost the oxygen evolution reaction (OER) is daunting. With the rapid decline in fossil fuels, energy research is turning toward water splitting to produce usable hydrogen by significantly reducing overpotential for other half-cells' OER. Recent studies have shown that in addition to the conventional adsorbate evolution mechanism (AEM), participation of LOM can overcome their prevalent scaling relationship limitations. Here, we report the acid treatment strategy and bypass the cation/anion doping strategy to significantly enhance LOM participation. Our perovskite demonstrated a current density of 10 mA cm-2 at an overpotential of 380 mV and a low Tafel slope (65 mV dec-1) much lower than IrO2 (73 mV dec-1). We propose that the presence of nitric acid-induced defects regulates the electronic structure and thereby lowers oxygen binding energy, allowing enhanced LOM participation to boost OER significantly.

Modulation of the optical bandgap and photoluminescence quantum yield in pnictogen (Sb3+/Bi3+)-doped organic-inorganic tin(IV) perovskite single crystals and nanocrystals.

Water-stable, lead-free zero-dimensional (0D) organic-inorganic hybrid colloidal tin(IV) perovskite, A2SnX6 (A is a monocationic organic ion and X is a halide) nanocrystals (NCs) with high photoluminescence (PL) quantum yield (QY) have rarely been explored. Herein, we report solution-processed colloidal NCs of blue light-emitting T2SnCl6 and orange light-emitting T2Sn1-xSbxCl6 [T+ = tetramethylammonium cation] from their corresponding single crystals (SCs). These colloidal NCs are well-dispersible in non-polar solvents, thereby maintaining their bright emission. This paves the way for fabricating homogeneous thin films of these NCs. Due to organic cation (T+)-controlled large spin-orbit coupling (SOC), the T2Sn1-xSbxCl6 NCs exhibit bright orange emission with an enhancement in PL QY of 41% compared to their bulk counterpart. Furthermore, we explore T2Sn1-xBixCl6 and T2Sn1-x-yBixSbyCl6 SCs, which show blue and green emission, respectively; the latter is attributed to the newly formed Sb 5p and Sb 5 s orbital-driven band structures confirmed by applying density functional theory (DFT) calculations. The SCs and NCs exhibit excellent stability in water under ambient conditions because of the in-situ generation of a hydrophobic and oxygen-resistant passivating layer of oxychloride in the presence of water. Our findings open a pathway for designing lead-free perovskites materials for thin-film-based optoelectronic devices.

Multiphotoluminescence from a Triphenylamine Derivative and Its Application in White Organic Light-Emitting Diodes Based on a Single Emissive Layer.

White organic light-emitting diode (WOLED) technology has attracted considerable attention because of its potential use as a next-generation solid-state lighting source. However, most of the reported WOLEDs that employ the combination of multi-emissive materials to generate white emission may suffer from color instability, high material cost, and a complex fabrication procedure which can be diminished by the single-emitter-based WOLED. Herein, a color-tunable material, tris(4-(phenylethynyl)phenyl)amine (TPEPA), is reported, whose photoluminescence (PL) spectrum is altered by adjusting the thermal annealing temperature nearly encompassing the entire visible spectra. Density functional theory calculations and transmission electron microscopy results offer mechanistic understanding of the PL redshift resulting from thermally activated rotation of benzene rings and rotation of 4-(phenylethynyl) phenyl)amine connected to the central nitrogen atom that lead to formation of ordered molecular packing which improves the π-π stacking degree and increases electronic coupling. Further, by precisely controlling the annealing time and temperature, a white-light OLED is fabricated with the maximum external quantum efficiency of 3.4% with TPEPA as the only emissive molecule. As far as it is known, thus far, this is the best performance achieved for single small organic molecule based WOLED devices.

Directional Shuttling of a Stimuli-Responsive Cone-Like Macrocycle on a Single-State Symmetric Dumbbell Axle.

Rotaxane-based molecular shuttles are often operated using low-symmetry axles and changing the states of the binding stations. A molecular shuttle capable of directional shuttling of an acid-responsive cone-like macrocycle on a single-state symmetric dumbbell axle is now presented. The axle contains three binding stations: one symmetric di(quaternary ammonium) station and two nonsymmetric phenyl triazole stations arranged in opposite orientations. Upon addition of an acid, the protonated macrocycle shuttles from the di(quaternary ammonium) station to the phenyl triazole binding station closer to its butyl groups. This directional shuttling presumably originates from charge repulsion and an orientational binding preference between the cone-like cavity and the nonsymmetric phenyl triazole station. This mechanism for achieving directional shuttling by manipulating only the wheels instead of the tracks is new for artificial molecular machines.